Organo-tin compounds of organic amines



3,037,039 ORGANO-TEN (IQMPOUNDS F ORGANIC AMENES" Paul A. Mazur, Dumont, N.J., assignor to S e: M Chemi- 3,037,039 Patented May 29, 1962 methyl phenyl tin chloride, tri-p-nitrotolyl tin chloride, trinaphthyl tin bromide, tristyryl tin bromide, and the like. Besides the chloride, the anion may be another halogen, acetate, sulfate, bromide, formate, hydroxyacetate, m0no-,

di-, or tri-chloracetate, acid sulfate, monoalkyl sulfate, No fgijg g gf figg; %gf :fF monoor di-acid phosphate, monoor di-alkyl phosphate,

4 Claims. (Cl. 260-429.7) and the i Of particular value are the organometal derivatives pro- This invention relates to new compositions of matter duced by reacting organo-tin compounds with condensates comprising organo-tin compounds of organic amines. of oxirane compounds and amines of a rosin. In the More specifically, it deals with reaction products of ordistillation of turpentine oil, crude turpentine, turpentine gano-tin compounds with organic amines, including an oil or tall oil, a rosin type of residue is obtained, an densates of oxy compounds and amines of a rosin, and important constituent of which is abietic acid. From to non-therapeutic germicidal and fungicidal composithis residue there may also be obtained, by well-known tions containing the same. methods, dehydroabietic acid and other rosin compounds. Among the organic amine compounds useful for prepa- Such rosin and rosin compounds (all of which will be ration of the organic tin compounds of the present inreferred to as rosin) y be aminatfid, y methods vention are included the primary, and/ or secondary familiar in the art, to produce amines which are marketed and/or tertiary amines of the aliphatic, aromatic, hycommercially as rosin amines. droaromatic, alkylaryl, and heterocyclic species, as Well as R l a s have b und t se With 0011- polymeric amines. The amines may contai y, halo, densible organic compounds containing an oxirane radi: sulfur-containing (mercapto, etc), imine, glyoxalidine, cal to produce condensates of various structures and comhydroxy, and/or quaternary o i h N,N- positions, depending upon the nature of the compounds diethylaminoethyl-N,N,N-tri-methyl ammonium chlocondensed, their P QP and the number of moles ride) and other organic substituent groups. Examples of and/or types of and/01 condensible Suitable amino compounds are 2 amino 2 ethy1 13 pounds involved in the reaction. For example, when propanediol, amines sold commercially under the dehydmabletylamme which as F (.mmmerclany Ethomeembrand, exemplified by under the trade name ROSID. Amine D, 1s condensed C12H25NH(C2H4O)4C2H4OH w th ethylene oxide (II), there are formed an N-sub- 3Q stituted monoethanol derivative (III), an N-substituted (Ethomeen C45), 12 2s z 4 )9 2 4OH O- diethanol derivative (IV), and polyethylene glycol ethers mean C), 12 2s 2 4 2 4 (Ethomeefl of the diethanol derivative (V), roughly in accordance 12 25 2 4 )14 2 4 (1511101115611 with the following reaction:

CH; CHjNHg and C H NHC I-I OC H OH (Ethomeen Sl2), heterocyclic compounds containing reactive primary and/or secondary and/ or tertiary nitrogen atoms within the nucleus or on substituent groups, diethanolamine condensates, such as diethanolamine-coconut fatty acid condensate, triallyl amine, triethanolamine, pyridine, tris (hydroxymethyl) amino methane, amines sold under the Armeen brand, as exemplified by (C H NH (Armeen 2-C), dimethylaniline, amines sold under the Duomeen brand, as exemplified by C H NHC I-I NI-I (Duomeen- T) and C H NHC H NH (Duomeen C), l-auryl dimethyl amine, tris (hydroxymethyl) aminomethane [(CH OH) CNH and the like.

The organo tin compounds to be reacted with the amines include quaternary organo-tin compounds in which tin atoms are attached directly to alkyl, aryl, alkylary-l, alkenyl, al-kynyl, alkadienyl, alkatrienyl, alleapolyenyl, alkapolyenynyl, alkenynyl, substituted aryl, substituted arylalkyl, hydroxya'lkyl or alkoxyalkyl groups and combinations thereof, as exemplified by tributyl tin chloride, triallyl tin chloride, trimethallyl tin chloride, tribenzyl tin chloride, triphenyl tin chloride, ethoxyethyl dibutyl tin on 41h on, QH,

These condensates or adducts are being marketed commercially under the trade name Polyrad. R represents the dehydroabietyl-amine radical, less the amino group.

The present invention involves reacting these latter condensates or adducts with an organo-metal moiety containing tin to produce highly valuable compounds suitable for non-therapeutic use in fungicidal, bactericidal, insecticidal, algaecidal, phytocidal and other such compositions. Broadly, such compounds may be represented by the formula:

( b c) m wherein R represents an organic group of the class consisiing of alkyl, alkenyl, alkynyl, aralkyl, aryl, alkadienyl, alkatrienyl, alk-apolyenyl, alkapoyenynyl, alkenynyl, substituted aryl, substituted arylalkyl, hydroxyalkyl, and alkoxyalkyl radicals, Sn represents an atom of tin originating from an organo-tin anion compound, said atom being attached directly to a carbon atom of R, Y represents an amine adductive with Z, Z represents an adductive compound containing an oxirane group, reactive with Y, X represents an anion when originating from said anion compound, b is a numeral ranging from 1 to 140, representing the mol-al-proportion of Y employed in the reaction, 0 is a numeral ranging from 0 to 40, representing the molal proportion of Z, while m is a numeral ranging from 1 to 3.

From the foregoing, it is apparent that b and 0 need not be whole numbers and that c may be zero, in which case the last-given formula would be written as:

( a b) m When Y is a primary or secondary amine reacting with R SnX, an amine salt of the organo-metallic compound is formed. Tertiary amines, upon reaction with metalloorganic compounds bearing an anion, produce with said metallo-organic compound a quaternary compound.

As examples of the type of organic groups which have been found, useful for the radical R, are methyl, ethyl, propyl, butyl, lauryl, allyl, methallyl, propargyl, benzyl, ethoxyethyl, hydroxy-ethyl, hexadienyl, linolenyl, octadecyltetraenyl, diocetylenyl, octadecyltetraene-IS,16-ynyl, phenyl, octynyl, p-chlorophenyl, tolyl, p-trifluoromethylphenyl, p-nitrotolyl, naphthyl, styryl and the like radicals. Compounds suitable as Z compounds include ethylene oxide, propylene oxide, butylene oxide, butadiene dioxide, styrene oxide, epichlorohydrin, and the like. Although as tributyl tin chloride (hereinafter referred to as TBTC), with the organic amine, followed by heating for about two hours in a suitable vessel. The product may be employed as such, or purified by conventional methods for use in agricultural and industrial outlets. Rosin Amine D" will be indicated herein as RAD.

The examples given in Table I illustrate many of the novel phases of the present invention. The first column after the example number lists the amount of tributyl tin chloride (TBTC) reacted with the specified amount of amine in the next two columns. The following column specifies the physical state of the reaction product, while the succeeding column indicates the molecular weight of the reaction product. In the last column, the germicidal activity of the reaction product is specified as the average of three experimental values. The data were obtained by steeping for minutes cotton disks mm. diameter) in a 0.1% alcoholic solution of the gennicide, rinsing, and drying. The disks were then placed in Difco nutrient low molecular Welght condenslble Y Compounds of 20 agar seeded with S. aureus (24-hour culture in nutr1ent molecular weight below about 200 are most desirable, broth) and vthe plates were incubated at 37 C. for 24 higher moleculaf Wlilght cOIIIPOUIIdS y be p oyed. hours. The zones of 1nh1b1t1on around the disks were The preferred method for the preparation of the commeasured in millimeters.

Table l Inhibi- Example 'IBTO, Amine Gm. State Vol. lion No, gm. Wt. Zone,

13 2-arnino-2-ethyl-1,3 pro- 1. 8 Waxy solid-. 414 16 pauediol. 13 "Ethameen C- 16.2 Liquid 730 14 32.5 Diot hanolarnine-laurio 30.5 .-..-do 630 14 ac l3 'Iriallylamlne 5.5 -do 402 12 13 Trietlmnolamine- 5.9 Waxy solid. 474 13 26 Pyridine 6. 4 Liquid 40-1 12 13 Tris (hydroxymethyl) 4. 8 Waxy solid 4 16 14 amino methane. 8 13 Arrneen 2-6 14.1 12 9. 13 Ethorneen C-. 1-1 10 13 Ethomeen C-1 2. 10. 8 12 1 13 Ethorneen Sl2-- 14.1 1-1 12 13 Duolneen T--. 13 12 13 13 Dime thylaniline. 4. 8 11 14 13 Lauryl dimethyl a: 8. 5 12 15 13 Etliomeen C-25- 33. 8 12 16 13 Duorneen C 9. 7 12 17 32.5 RAD Polyrad 0515 48.5 Liquid 11 pounds of the present invention lnvolves the mixing of It W111 be noted that all of the compounds listed in the required quantlty of the organotm compound, such Table I are very effective germicldes.

Table II Solubility Relrac- Specific Exaln- Organo-Metalhc Gm. Condensate Gm. tive Gravity ple No Index at (20 C.) Etha- 15 0. ml Water (1:00)

32.5 RAD+5 molEpichlorhydr-in 78.0 Insoluble. 32.5 RAD+1 molStyrcne oxide... 43.6 D0.

8.1 RAD+2O mols Proplyene oxide 39.2 Dispresible, 32.5 RAD+31T101S Propylene oxide. 49.0 Insoluble. 32.5 RAD+4 mols Propylene oxide.. 54. 8 Do. 32. 5 RAD+5 mols Propylene oxide- 60.7 Dispersible. 32.5 RAD-l-S mols Propylene oxid 78.1 Do. 16. 3 RAD-H0 mols Propylene oxid 44. 9 Do. 16.3 RAD-H1 mols Propylene oxide. 47. 8 Do. 32.5 RAD+1 rnol Butylene Oxides S 38.8 Do. 32.5 RAD+5 mols Butylene O des 67.6 32. 5 Rosin Amine D- 31.13 Insoluble. 32.5 Polyrad 0100- 30.0 D0. 325 Polyrad 0200. 40.2 D0. 32.5 Polyrad0500. 53.5 Dispcrsible. 32.5 Polyrad 0515. 48.5 Do. 32.5 Polyrad 1100. 79.9 Soluble. 16.3 Polyrad20UOL 66.5 Do. 8.1 53.0 Do. 32.5 RAD+1molM1xe Butylene es. 38.8 Insoluble. I 32.5 RAD+5 mcls Mixed Butylene Oxides. 67.6

27.7 Polyrad 0515 48.5 Dlspersible. chlorlde. Trlrnethallyltin 31.9 Polyrad"0515 48.5 Do.

chloride. Trlbenzyltin 42.7 Polyrad 0515 18.5 Do,

cholride. Triphenyltin 38.5 RAD-l-Polyrad 0516 48.5 Do.

chloride.

Other effective materials derived from RAD and Polyrad compounds are listed in Table II. The second column of Table II specifies the organotin moiety (R 811) and gives the weight thereof used, Whereas the third column specifies the nature of the condensate moiety (YZ) and gives the weight thereof used. The remaining columns give the properties of the invention product obtained. Unless otherwise noted, the product is a liquid. Butylene Oxides 5 represents a commercial mixture of straight chain butylene oxides. The numerals after Polyrad are commercial designations.

The effectiveness of the germicides of the present invention, in comparison with other commercial germicides, is given in Table HI. Here, toxic dilution tests for fungistatic and bacteriostatic activity were made in triplicate, using alcoholic solutions of the germicides ranging from dilutions of 1000 p.p.m. to 0.01 ppm. Paper disks mm. in diameter were steeped in the solutions, rinsed and dried. Petri dishes seeded with each organism in nutrient agar were inoculated for 24 hours at 37 C. with these disks and the lowest concentration having germicidal activity was recorded in the table. The results, in parts per million, are given for the five germicides tested as follows:

Table III Com- G11 pound Grade of Salicyl- 2, 4, 6 Tri- Orgauism N o. 17 of Hexa- TMTD 1 anilide chlor- Table I chlorophenol phene S. aureus 0.1 2 25 50 3 S. aZbu8 0.1 2 25 50 3 B. sulltilis O. 1 2 35 45 3 L casez'. 0.1 10 50 45 3 S. faecalz's. 1.0 40 35 50 3 A. aeroganes. 1.0 10 50 45 200 0.1 10 50 50 3 0.1 50 50 50 3 O. 1 40 50 50 3 0.1 40 25 45 200 A. niger 0.3 50 50 50 20 P. ezpansum. 0. 05 50 50 50 30 T. mentagrophytea 0.05 50 50 20 1 TMTD=Oomrnercia1 grade of tetramethylthiuram disulfide.

Among the uses for the compounds of the present invention are the control of mold and slime in paper pulp, the control of mildew on burlap or paper bags and on canvas, the control of thrips and aphids on roses, as well as control of bacterial and fungal diseases of bushes and trees. Other uses include rodenticide compositions, compositions for the sanitizing of rugs and upholstery, the mothproofing of woolen fabrics, and the control of such insects as carpet beetles, silverfish, and the like. For such uses, the compounds are preferably dissolved or dispersed in an aqueous medium in the concentrationof 0.05 to 1%, or even 5% or as much as 10%, depending on the type of lasting effect to be retained or the price considerations involved. Solubilizers such as alcohol, glycol ethers or esters, ketones, and the like, maybe added to the solutions when this phytocidal action is not a factor. In cases where water is objectionable, the germicide may be dispersed in a non-aqueous solvent such as naphtha or chlorinated hydrocarbons. The germicides disclosed herein have been found to be effective against gram-positive and gram-negative bacteria, fungi, algae, *and against a large number of insects and other types of parasites.

It has been found that the most suitable germicides of this invention are obtained when reacting the anion-bearing organo tin compound with an organic amine com pound having a molecular weight between 31 and 6000, preferably between 50 and 1500.

This application is a continuation-in-part of copending application Serial No. 647,739, filed on March 22, 1957, by Paul A. Mazur, and now abandoned.

I claim:

1. A composition of matter comprising an organometallic compound having the formula:

wherein R represents an organic hydrocarbon group consisting of alkyl, alkenyl, aralkyl and aryl radicals having 4 to 18 carbon atoms, Sn represents an atom of tin originating from a tri-organo tetravalent tin anion compound, said atom being attached directly to a carbon atom of R, Y represents a rosin amine adductive with Z, Z represents an alkylene oxirane compound reactive with Y and having a molecular Weight of 44 to about 200, X represents a halide anion originating from said anion compound, b is a numeral ranging from 1 to 140, representing the molal ratio of Y, c is a numeral ranging from 1 to 40, representing the molal ratio of Z, and m is a numeral ranging from 1 to 3.

2. A composition of matter according to claim 1 comprising a tributyl tin-rosin amine-ethylene oxide condensate.

3. A germicidal composition containing a non-therapeutic material subject to deterioration by microbial action and 0.05% to 10% of an organometallic compound of an anion-bearing tri-organo tetravalent tin compound and a condensation product of a rosin amine with an alkylene oxide of molecular weight below about 200.

4. A germicidal composition containing a non-therapeutic material subject to deterioration by microbial action and 0.05% to 10% of an organometallic compound of tributyl tin chloride and a condensation product of rosin amine and ethylene oxide.

References Cited in the file of this patent UNITED STATES PATENTS 2,510,284 Haggard June 6, 1950 2,580,473 Sowa et a1. Jan. 1, 1952 2,772,260 Yeager Nov. 27, 1956 

1. A COMPOSITION OF MATTER COMPRISING AN ORGANOMETALLIC COMPOUND HAVING THE FORMULA: 